Magnesia-alumina-silica refractories



June 3, 1952 F. E, A-[HE 2,599,184

MAGNESIA-ALUMINA-SILICA REFRACTORIES Filed DGO. 24, 1949 2 SHEETS-SHEET 1 gli mi] H Ffn/ 1.62272@ INVENTOR.

June 3, 1952 F. E. LATHE 2,599,184

MAGNESIA-ALUMINA-SILICA REFRACTORIES Filed Dec. 24, 1949 2 SHEETS-SHEET 2 slo2 11mm AYAYQNYA Patented June 3, 1952 MAGNESIA-ALUMINA- SILICA REFRACTORIES Frank E. Lathe, Ottawa, Ontario, Canada, assignor to Canadian Refractories Limited, Montreal, Quebec, Canada, a corporation of Canada Applicationl December 24, 1949, Serial No. 134,930

This invention relates to a method of consolidating granular particles of refractory material, at a temperature lower than heretofore possible, into a -highly refractory and mechanically strong or load-bearing product, which consists essentially ofv magnesia and silica and for most applications contains an appreciable amount of alumina.

In accordance with the present I invention granular particles of refractory material containing a total of at least 80% by weight of magnesi'af silica and alumina, and in which the Weight ratio of magnesia to silica and alumina is at least equivalent to 1.5 times the silica plus 0.5 times the alumina, are mixed with a relatively non-refractory material, preformed or natural, containing at least 75% by weight of magnesia, silica and alumina, of which substantially 35 to 82% is silica, 0 to 40% is magnesia, and 0 to 50% is alumina. It will be observed from the magnesia-alumina-silica phase equilibrium diagram which accompanies this application (Figure l) that Acomplete reaction between the above components of the non-refractory material, within the limits of composition given, leads in every case to the formation of low-melting silicates, with no magnesia present as periclase. This is essential in order that the non-refractory constituent will form a substantial body of liquid at a temperature of 1500u C. or less. The refractory and non-refractory constituents are mixed in such proportions that the amount of magnesia in the final mixture is not. substantially less than 1.34 times' the silica plus 0.40 times the alumina in order to insure that there is present magnesia in quantity at least sufficient to convert all of the silica to magnesium ortho silicate (forsterite) and all of the alumina to magnesium aluminate (spinel). The mixture is heated to a tempera-l ture higher than that of incipient fusion of the non-refractory constituent. As the latter melts it reacts with the magnesia of the refractory constituent to form forsterite (2MgO.SiO2) and spinel (MgO.AlzO3), both of which fuse only at much higher temperatures, and which with magnesiavform no eutectic melting below 1700c C. As heating is continued, the non-refractory constituent is eliminated by reaction with the refractory granular material, and the result is a bonding together of the refractory granules to a load-bearing structure whichdoes not even soften except at an extremely .high temperature.

f Inf'order to secure the benets of the invention itis essential to select both the refractory granu:

1an-material and the relatively non-refractory.

` 17 Claims. (Cl. 10G-62) material to be used'within the particular composition ranges given. l

Because of the tendency of calcareous materials to react with aluminous materials and form low-melting products whichy cannot be eliminated by heating with materials high in lime or magnesia, it is important that both the refractory and non-refractory constituents used in the practical application of this invention should be relatively low in lime. For the highest refractoriness in the product they should be entirely free from lime, but such raw materials as sea-water periclase, Washington, European and Manchurian magnesites, are, as marketed, suiiiciently low in lime to permit their use, either as the refractory granular material to be bonded or in the preparation of the low-melting constituent to act as a bond. The presence of 1% of lime in the final product `may result in the formation of 6 to 7 of liquid when the temperature is raised to 1700o C., but for many applications this is not particularly objectionable. In other applications it is advantageous to have all raw materials substantially lime-free.

Other impurities than lime are often objection-y able if present in more than minor proportion, butthe normal magnesias mentioned above are satisfactory in this respect. Within the limits already set out above, silica'and alumina in the refractory constituent are not objectionable, and in the non-refractory constituent they are relied upon to form a low-melting material with the magnesia.

A characteristic of mixtures of the typecoming within the scope of this invention is that when exposed to temperatures at or above the melting point of the non-refractory constituent they: first become pasty, as this constituent melts, and then stiifen up as the reaction proceeds with therefractory granules; eventually the whole mass be-- comes quite hard, Within wide limits, the higher the temperature used, the harder will be the product, the reason being that progress towards ultimate equilibrium is more rapid and more nearly complete at the higher temperature.

. The non-refractory constituent maybe one or :a combination of several natural minerals or rocks of suitable composition, or it may be preformed by anyl suitable method. Complete fu's'ion can readily be brought about by heating raw materials of the `desired over-all composition and? physical character in `water-jacketed blast furnaces (when coarse)A or in 'reverberatory or electric furnaces (whether coarse orj fine):A Granulation in' water is a .cheap and convenient means of converting the non-refractory material to a suitable grain size. Fusion can, if desired, be brought about in rotary kilns, but when these are used it is customary to carry out the operation at such a temperature that sintering, shrinkage and nodulization of the fine charge occur without complete fusion. In such a case the reaction does' not usually proceed to complete equilibrium, but sufficient liquid is formed to act as a strong bond upon cooling. After beingcooled, the fused or clinkered product is crushed to the desired grain size for use as a non-refractory constituent in the bonding of the refractory granular material.

It has been found that the best results are obtained When the non-refractory constituent is substantially of a grain size within the rangek 6 to 20 mesh. When the material is coarser, drainage of the non-refractory constituent prior to reaction with the granular refractory is more likely to occur; when itis too fine (especially if fine material also occurs inthe refractoryc'onstituent) the Yreaction may take place sorapidly that insufficient liquid exists atany one time to shrink the particles properly and bond them strongly togethen Thus the use -of /very fine materials may resultina product which, while equally refractory, is relatively soft,- and hence not satisfactory with respect to mechanical strength. The use of fine particles of non-refractory constituent is not objectionable when fines have been removed from the refractory port1on.

Since the invention comprises a method of consolidating granular particlesA of 'refractory material, it follows that thismaterial must not be wholly fine. There is, however, a considerable range of particles size which gives good results. For example, fettling materials sometimes consist of vat least 50% byV weight of particles coarser than 1A", whereas in manufacturing brick' it is customary to crush the raw materials'until' sub-Y stantially all' particles are below 1A", or insome cases even below g'i' Refractory materials to be bonded should preferably contain at least 50% by weight of grains coarser than mesh.

The operation' of the invention isillustrated by reference to the accompanying'drawings in which,

Figure 1 is a simplified form ofthe phase equilibrium diagram'of the'ternary system magnesia-V alumina-silica, as published by the'United States Steels Corporation, revised edition, April, 1943;

Figure 2 shows, for the same system, the ranges of composition of the non-refractory material of the invention which are (l) 100% and (25 75% liquid at 1500 C., and

Figure 3 particularly designates on the diagram the limits of the non-refractory material specifically defined herein and also the limits of composition of the refractory granular particles to be' bonded.

These drawings Vfacilitate a ready understanding of the scope of 'theinvention It will be observed (a) that the composition of the granular refractory material; on the basis of its content of magnesia, alumina and silicaonly, has a proportion of magnesia at least equal to 1.5 timesY the'silic'a and 0.5 times the alumina, as lshown byline 2, Figure 3, and lies appreciably below the forsterite-spinel join, line I on the diagram, and accordingly has Vexcess magnesia above that required to form :forsterite and'spine'l, which excess will combine with the silica and alumina of the nonrefractory'v lnaterial,l and (b) that thec'omposition of the non-refractory material' used'to 4 consolidate the refractory granules lies substantially within the hexagonal area A shown in Figure 3, and preferably Within the hexagonal area B of the same figure. The forsterite-spinel join, line I Figure 3, corresponds to compositions in Whichthe amount of magnesia is 1.34 times thesilica plus V0.40 times thejalumina'.

' 'y Example v1 rlTnere is available in the form of granular ,refractory particles a synthetic material containing substantially 40% magnesia and 60% alumina, and it is desired to make a brick of this material Yhaving a strong ceramic bond, such as could not bev secured from the particles alone Without burning the'- brick at an excessively high temperature. There is also'available, as a lowrnelting constituent, a siliceous talc containing substantially 16 MgO, 74 SiOz, 7 FeO, 1 A1203, 1 CaO and 1% loss on ignition. It will be observed that thel constituents magnesia, silica and' alumina are present in the proportions'l, 81,3jand.

1.1% respectively, gaY composition corresponding closely to cornerv z of theh'exagonalareafA 'of Fig. 3. The siliceous talc, partly because of the presence of the minor quantities of impurities, forms some `liquid upon being heated to about 1350 C., and is substantially all moltenat`1500. This material is crushed until at least 50% Tof it will pass a 6 mesh screen and be retained `on 20 mesh, and 10 parts of it are mixed with 90 parts of the refractory granular particles which have been prepared by crushing them s'o' that 60% is minus 6 plus 65 mesh and 40% minus 65 mesh. The whole is moistened with wateranda suit-1 able temporary bond, such as a concentrated lig'nin liquor, tempered ina wet pan and .molded into brick, as in ordinary brickimakingy 'prac` tice. The brick are `then burned atlll Before this temperature has been reached sub*- stantially all the non-refractory constituent has been converted to liquid; this then gradually'rei acts with Vthe excess magnesia'of the refractory granules and is itself eliminated through the formation of refractory compounds. The 'final composition, on the basiszof the magnesia, alud mina and silica only, is :about 371.9 magnesia, 54.6 alumina and 7.5% silica.- This composition is not appreciably affected by *theV impurities ofthe siliceous talc, and the burned brick'contains substantially only spinel and forsterite, 'whichto gether form no Vliquid below 1700* C., 'and in the proportions present Would not be wholly molten below 2000u C. By the method described there is produced at the ordinary temperature of burn* ing, a ceramically bonded. brickof exceptionally high refractorine'ss.

Example 2 It is desired to use in the formation 'of a re# fractory brick a granular sea Water periclase con-V taining substantially 93 magnesia, 5 silica and 2% lime. (For purposes of calculation, this may be taken as 95 magnesia and 5 silica.) YIt has been crushed until 20% remains on 6 mesh and about 25% is nner than 100 mesh. Its refractorine'ss is Aso high that it cannot be burned alone' to 'a hard-'dense brick except at 1600` C. or higher. In order to `p'errnitbu'rnng at a lower temperature, there are mixed with '15 parts of thegranular seafwater refractory' 25 partsl of minus 6 mesh gremita; Vwhich contains 2.6 Mge,Y '13.0 A1203', 71.1 SiOa,2.5 Feas, 1.8 FeO', kk2.0 Caf), 410 Naz() and"'320% K'zO. that is,lmagnesia, 'alumina and silica substantiallyin the proportions'3,'15 'and 82%, respectively. 'I'.hese three constituents alone, which irr4 Acomposition l' correspond closely to?corneryif.thehexagonal area A of Fig. 3, wouiduin combiaticnform '15% liquidar 15oo C.,.fa'nd, actually," becauseof minor amounts of alkaltilironand." other oxides present, begin to nielt'rb'elow ',1300 andare wholly molten at about 1 450FC;r Mixed vwith `the highly refractory sea water periclase' andl formed into brick by the' usual means, the granite melts as above and then reacts with the periclase to form a mechanically strong. brick consisting; essentially (neglecting impuritis) of ,724 magnesia, 3.8 alumina and 24.2% silica, 'or 5.2.fspinel,l 56.5 forsterite and 3,8.3%..periclase, which combination forms no liduid'below Y1'700 andis not 4Wholly molten below 220-0"C" In this .cafse,fsyenite or diorite may be satisfactorilysubstituted for granite, provided that they arenot undesirably high in lime, but the flr'llprdductwill then have a slightly different composition. t y Y Erample 3 l:A7 refractory granular material containing abutto magnesia, alumina and 5%l silica is required tombe bonded at 'the lowest feasible temperature atmechanically@strongy and modrately refractorily lining fora laboratory furnace. a` bonding' material there is selected nepheline syenite containing 60 silica and 24% alumina; it also contains'l enough soda and potash to lowerA the fusion point to about 1250 C. while initialliquid formation takes place below 1050. Tiflis-isV used after crushing to mesh, and is incorporated to the extent of 15% of the total mixture. The mixed material is burned-in at 1250--1300o C.,Aat which temperature a very strong ceramic bondis developed, and 'at ultimate equilibrium the major constituentsl magnesia, alumina and Isilica-are present in proportions 69.6, 16.8 vand 13.6%, respectively. These alone form no liquid below 1700 C., and, while appreciable quantities of alkalies occur in the low-melting constituent, these constitute only about 2% of the finalv mixture, and do not detract from its value as av refractory for use at moderate temperatures.A f

' i Example 4 There has` been prepared from a naturally ocalumina and 60% silica until all jpasses 6 meshY and about 35% passes 20 mesh. Actually, minor proportions of other oxides in the grog, amount-- ing to a total of about.5%, cause it to form ini-l tial liquid below 1400 and about 80% of liquid at 1500" C. The grog bonds the mass strongly'when, upon heating the brick to 1500 C., it melts and reacts with the granules to form spineland' forsterite. The impurities in the grog, it will-be observed, constitute only 0.4 of-the final brick. The over-all chemical composition is substantially 83 magnesia, 7 alumina and 10% silica,'and

the corresponding mineralogical composition is 9.6 spinel, 24.1 forsterite and 66.3% periclase, one

which is again highly refractory. Good results are also obtained when the clay brick grog contains substantially equal propor- 6 tions of silica and alumina, in which case the composition approximates the corner :c of th hexagonal areaAof Figure 3. t

Granular magnesia almost% pure is avail able from careful selection and dead-burning of California magnesite, and it is desired to use this in making the monolithic hearth of Va. basic open hearth steel furnace. It is rst crushed to pass 4 mesh, in which form it contains 30% of minus 20 mesh material. yEighty parts of this highly refractory magnesite are then mixed" with 20 parts of minus 6 plus 20 meshv synthetic granules formed by sintering kyanite or bauxite, clay and magnesite to a product containing 15 magnesia, 50 alumina and 35% silica, andcrushing and screeningthe sinter. It will be observed from Figs. Zand 3 that this non-refractory product forms about 60%. of liquid even at 1500.C., and that its composition lies at the corner w of the hexagonal area A of Fig. 3. -The mixture of the two materials is then" thrown a little at a time into the open hearth furnace held at 165 0 C., and is burned-in according to the usual practice. Fusion of the synthetic constituent occurs almost immediately, and it strongly bonds the refractory particles of magnesite together as it reacts with them and is itself eliminated., The Yultimate product contains substantially 83 magnesia', A10 alumina and 7% silica, a composition which does not completely melt below 2600 C.

It is of interest to contrast such a hearthwith one prepared in a similar way from mixtures of magnesite and open hearth slag, which is already highly basic, as has long been customary in the steel industry. In the slag, all of the acid constituents (including SiOz, P205, A: and FezOa) are already present in combinations with lime from which they cannot be displaced by Amagnesia. The result is that no appreciable reaction takes place between themagnesite and slag, and, after burning is completed, the hearth-still consists of particles of periclase embedded in slag of substantially the original composition. Thelat-K- ter will still melt at ordinary open hearth temperatures, and the bottom is therefore susceptible to physical erosion, whether from solid charge dropped into the furnace or from one of the occasional boils which, if not stopped by prompt tapping of the heat, often make a hole completely through the refractory lining and result in loss of the heat through the bottom. It will -be recog niz'ed .that much greater resistance is offered to the' action' of a boil when the refractory bottom is formed by the method and materials described in this example, andas a consequence of the elimination of liquid' retains a Asubstantial proportion :of its mechanical strength even at the highest open hearth temperatures.

. Example 6 1 4 It risalsov evident that the same combination Ao f materials used in Example 5 can be applied in forming a refractory ramming mixture for use .in open hearth or electric steel furnaces. In this case it is desirable to have about 50% of the granular refractory to be bonded crushed to pass 2&0 or even 40 mesh, in order that suiilcient fine@k may be present `to permit ramming the mixture to a mass of high density, but it is still desir tohave the non-refractory material presen larger granules, such as the minus 6 plus 20 sitze previously specified. A bottom, of vth Example 7 -In thisexample, the granules contain SO-magnesia, 10 aluminarand 10% silica, and the lowmelting'bonding constituent is made by fusing 40 parts of serpentine with 60 of nepheline syenite. rIhis combination gives the three constituents magnesia', alumina and silica (which constitute about 90% `of the total weight) in almost the exact proportions of' the eutectic melting at 1347" vC.20.3, 18.3 and 61.4%', respectively, and

the composition' is therefore a particularly favourable one 'for use as a bond at low temperatures. After being melted,` it is granulated in water, as a convenient means of reducing it to substantially 'the desired grain size. Used in the proportions of one part to four of granules containing 80l magnesia,'10 alumina and 10% silica it produces a highly refractory material having thesek oxides present in proportions 69.5, 11.2 and 19.3 ,respectively Emmpze s Another eutectic Vin the magnesia-alumina-` silica system, melting at 1362 C. and containing magnesia, 21 alumina and 54% silica, can be .closely approached in composition by sintering or melting together equal parts of natural olivine and kaolin. When l2 parts of this product are used to-bond88`parts of granules containing 60 vmagnesia, r alumina and 10% silica, fusion of the non-refractory constituent is 'easily eiected, and the-product contains the same oxides in substantially the proportions 56, 29 and 15% respectively. Such a composition can be fused to a liquid only at labout 2000 C.

As will be evident from the magnesia-aluminasilica phase equilibrium diagram (Fig. l) serpentine, *talcr or enstatite can be substituted for the olivine, and `any aluminum silicate containing of silica or more for the kaolin, and equal proportions by Weight will still produce upon fusion a non-refractory constituent forming a high proportion of liquid even below 1400" C. Such low-melting materials are therefore particularly easy to make. f

Example 9 Suitable non-refractory constituents can. also be madesubstantially withoutA alumina. For example, When serpentine, which is available as a waste product in the asbestos district of Quebec and contains about 38% each of magnesia and silica, is' heated with enough silica to change the ratioA of theseoxides from :50 to 35:65, the

Acom-position of the 1547 eutectic between clinoenstatite (MgO.SiO2) and silica is reached, and the effect of the iron oxide in the impure serpentineis to reduce the melting point below 1500" C.

The composition in question is close to the corner u of the hexagonal area A of Fig. 3. Using 15% the product With 85% of synthetic granules containing 50% each of magnesia and alumina -gives"proportionsofv magnesia, alumina and silica approaching 2000 C.. with initial Aliquid formation about 1700. In thisy case itis not .essentialtovform the exact compositionof the 1547 eutectic between magnesia and silica-and good resultsare in fact obtained wheny the. silica .contentr of the non-refractory constituent. on `thebasis of mag-fv nesia and silica only, is kept in the range: 60 to 70%. Obviously; any other magnesiumv silicate maybe substituted for. the serpentine'.

Example 10 In forming the non-refractory constituent it' may be convenient. to userthree or more raw ma,-

terials, and one ofV these may in fact conveniently4 have the same composition `as the granules tolbev bonded, as when a particular grain size' of thisl refractory material is available in excessof the requirements for other purposes. when the refractory granules contain magnesvia, l15 alumina and 5% silifca,v50v parts may be fused with-30.6. parts o'f silica and'19.4"of a calcined bauxite containing alumina andv 10% silica to a non-refractory product with 40 magnesia, 25 alumina and 35% silica.- composition-is at the corner v `of the hexagonal areal A ofFig.- 3. If, then, 25 parts of. this low-melting material are used to bond 75 parts by Weight of the original refractory granules, the. ultimatey product will contain substantiallyY 70 magnesia. 17.5 alumina and 12.5% silica, whichA willattain complete liquidity only at about 2350 C., and

Will form no liquid below 1700.l In this case, three highly refractory materials, of whichY one has the same composition as the granules to be bonded, have been combined to form. the nonrefractory constituent, and this has in turn been eliminated by reaction with more of the refractory granular material. l

The above examples illustrate the very broad scope of the invention andthe limits of composition of the non-refractory constituent within which ,good ,results have been obtained. These limits may be defined as comprising all compositions which, onthe basis of their magnesia, al-umina and silica contents alone (that is, neglectmg minor proportions of lime, iron oxide, etc.) lie within the boundaries of the rectilinearhexag.-- onal iigure A in the magnesia-alumina-silica phase equilibrium diagram (Fig. 3) vdefined by the corners having compositions (z) 18 magnesia, 0 alumina, 82% silica, (y) 0 magnesia', 18 alu.' mina, 82% silica, 0 magnesia, 50 alumina, 50% silica, (w) l5 magnesia, 50 alumina, 35% silica, (v) 40 magnesia, 25 alumina, 35% silica and (u) 40 magnesia, -0 alumina and 60% silica'. Compositions lying substantially outside 'this hexagonal area are too refractory to give "good results when used as herein described. I

The limits of composition ofthe non-refractory constituent, whether naturally occurring or preformedmay also be approximately defined as including all combinations of magnesia, alumina andsilica (with not more than 25% of all other compou-nds) Whichv are at least substantially 75% molten at 1500 C. (Fig. 2)

A` preferred, and somewhat smaller, range `of composition of the non-refractory constituent is that which, on the samebasis, liesv within `the boundaries of the rectilinear hexagonal'igurefB in thev magnesia-alumina-silica.pliaseequilibrluri diagram' (Fig. 3) defined by corners having the compositionsv (1).v 19 magnesia,"7 alumina,"l74%' Silica, 2) v mag-naamw alumina; 74% silica, (3) i7 magnesia, 37' alumina, 56%- silica, i215):- 17 magnetic., arf alumina; 4.6% sliica'rsifaz ma'g;

For example,

y For convenience in calculation" it has been as sumedin several of the examples that'the nonrefractory constituent consisted entirely of the oxides magnesia, aluminaJ and silica. It will be appreciated, however, that, when using commercial or natural raw materials, minor amounts of other oxides, such as those of calcium', iron,'ti-

tanium and the alkali metals, may be present. The invention is limited, howevento the-use of non-refractory constituents, whether natural or -s'yrnthetically preformed, which contain'atleast 75% of magnesia plus aluminaplus silica.

YIn none of the preformed non-refractory. constituents is any of the magnesia at ultimate equilibrium present as periclase. When they are rapidly cooled fromv the liquid condition, as by granulation in water, they formV a glass, and when slowly solidified they crystallize to kvarious silicatesiof magnesia and alumina, the nature 'of which depends upon the composition ofthe melt.. Inno case, however,' does the magnesia crystallize as periclase," andthis is important, since by. using magnesia only in the combined form'v itis possible to produce vmaterialsmwhich are at 'least Vsubstantially 75% liquid .at 1347- 15009L'C., instead of being only somewhat plastic even at much higher temperatures, as disclosed in the prior art. I

Itis evident that, while the' granular particles of refractory material to be bonded always contain a large proportion of oxide constituents in the magnesia-aluminaesilicalsystem', the presence of `minor proportions of other oxides, Vsuch vas those of iron, titanium and lime, is permissible.

The invention is limited, howevento the bonding of refractory granular materials containing at least 80% "byweight, on the dead-burned or loss-free basis, of magnesia, alumina and silica, and having a ratio'of magnesia to silica and alu- :nina at least equivalent to 1.5 times the. silica plus 0.5 times the alumina. Preferably, the basic granular material to be bonded should contain at least 10% of free magnesia'in excess of that required to form magnesium ortho-silicatewith al1 thesilica present and magnesium aluminate with' all theA alumina in the granules, and not more than 5% of lime;

Inregard to the proportions of the non- .refractory and refractory constituents to be used in any particular oase, it will be observed from the examples given that these may vary widely. In vthe magnesia-alumina-silica system, however, a denite limit does exist, and use can be made only of those mixtures of non-refractory and refractory constituents which, in their over-all composition, contain sufficient magnesia to form forsterite with all the silica present and spinel with all the alumina, that is, the weight ratio of magnesia to silica and alumina must not be substantially less than 1.34 times the silica plus 0.40 times the alumina. Such materials, if pure and fully reacted, form no liquid below about 1700 C. Were appreciably less magnesia present, the over-all composition would be above the forsterite-spinel join (Fig. l), and liquid would be formed in at least small quantities at a temperature of 1372 C. In the final product this is of course undesirable. To those'versed in the art, it is a simple mathematical problem to calculate the proportions of the two materials which -larV fields of application, but only to the bonding of refractory granular particles by the use of siliceous non-refractory materials of the par ticular .type .herein described.

'I'his application is a continuation-in-part of copending application S. N. 688,264, filed August Y3, 1946, now Patent Numberv2,568,237-, issued SeptemberlS, 1951.

What is claimed is:

l. A method ofv consolidating refractory granulaimaterial. into a mechanically strong and Yhighly refractory product which-comprises mixing refractory granular particles containing a total of at least by weight of V:magnesia silica'and alumina and not more than 5 of lime and in which the weight ratio of magnesia te silica and alumina is'at least equal to 1.5ftimes `the silica plus 0.5 times the alumina, with nonrefractory material containing a total of at least 75% by weight of silica, magnesia and alumina of which substantially 35 to 82% vis silica, 0 to 40% is magnesia, and 0 to 50% is alumina, the mixture of refractory and non-refractory materials having a weight ratio of magnesia to Ysilica and alumina at least substantially equal to'1.34 times the silica plus 0.40 times the alumina, and heating the mixture Ato a temperature higher than that of incipient rfusion of the-non-refractory material to form liquid and coat the particles of granular refractory material and by reaction eliminate the non-refractory silicate and thereby bond thegranules into a highly refractoryy and consolidated mass.

2. A methodof consolidating granular refractory material into a mechanically strong'Y and Vhighly refractory product which comprises forming an intimate mixture of two types ofmaterials, the first type consisting of basic refractory granular particles containing a totalof at leastV 80% byA weight of magnesia, silica'and alumina and not more than 5% oflime and in which there is at least 10%v by "weight of the granular particles of-free magnesiain excess of the amount required to formrmagnesium orthosilicate with all the silica and magnesium aluminate with all the alumina in the granules, and the second type consisting of non-refractory Isilicate containing a total of at least 75% by cipient fusion of the non-refractory silicate to form liquid and coat the particles of granular refractory material and by reaction with their free magnesia convert the non-refractorysilicate into magnesium orthosilicate and the alumina into magnesium aluminate and thereby bond the :non-refractory rial having a composition within the range (l) .19 magnesia, -7 alum-ina, 74% silica, (2V) "i magnesia 19 alumina, 74% silica, (3) '7 magnesia, '37 alumina, .56% '.S'la, (.4) ,17 magnesia, 37 alumina, 46% silica, v(.5) 32 magnesia, 22 alumina, .Y

46% silica, and .(6) 3-2 magnesia, .7 alumina, 61% silica, the yweight ratio of magnesia to A,silica Iand alumina in the mixture being at least' substantially equal to 1.34 times the Silica plus .0.40 times the alumina, and heating the .mixture to a tem ,perature higher than that .of incipient fusion of` the non-refr-actoifyV material to form liquid to vcoat and react 4with the said granular refractory material and consolidate the mass.

4. A method as .dened in claim 2 wherein the i refractory .gr-anular material consists essentially of periclase.

A5. A methodes denedin claim 2 wherein :the non-refractory silicate contains 2 .to 40% magfnesia in combined form .and none Aas periclase.

.6. ,A method asdefi-ned in claim ..3 wherein the Y non-refractory silicate consists essentially .of the magnesiaealuinina-sila eutectic melting at .about 13.471C. and containing ;.substantially 20.3 .magnesa 1.8.3 alumina :and .611.4% silica.

' 7. A method as .donned in .claim 3 wherein Y'the vno il-l'.ciractory silicate consists essentially ofzzthe masnesia-.aluminasilica eutectic melting at about 13.62 o. and containing substantially .25 magnesio, c2.1 alumina and '54% silica.

.8. A method :as defined in claim :2 wherein the .nonereircotory :silicate :is .at :least .one of a :group :consisting of granite., v.Syente .and diorite.-

9. A method as defined in claimfz 'whereinthe starting .materials :for .the .non-refractory silicate ,comprise substantially .equal proportions of.:an .aluminum silicate containing at ieast 45% Aof .silica and i.one of a ,group ...consisting .of olivine,

serpentine. :talc .and Lenstatite..

1-0. `YA method as k l cate is Lformed by heating :to a :temperature 'higher than that of incipient .fusion at .least one of =.a group consisting of rnatlll'alfrolivnc, serpentine, ytalc and .enstatite with dened in.claim.2 .-whereinthe times the alumina.

12 silica to bring the silica content of the hired ture Awith-inthe .range .601to 00%,. Y

. 11. A method as delinea in .claim .1 wherein the nonereiractory 4.material :is preformed by .at least incipient fusion.

1 2.. .A method as siened :in claim ,1l wherein .the non-refractory .material is at :least suhstanf -tiallyr'l-.o molten at 15.00

1.3...A method as siennes 'claim All wherein the filoni-refractory material is at .least substantially 10.0% :molten at 150.09 C..

14.. .A method as defined in claim ,il wherein the non-.refractory material is .gram-11ste@ ...1n water.

l5. .A method as donned in olaimfl :at

least 50% by weight of the granular refractory particles are coarser than 20 mesh.

1.6. A :method .as 7tlefxietl :in v.claim 1 wherein at .least .byweieht oi the .nonfrenactoryiiia terial -coarser than 20 mesh.

17.. A batch .material for the preparation of :refractory masses and shapes 'which comprises .an intimate mixture of two :types of materials. .the iirst type consisting of liiasic refractory gran- A111er particles containing a total .of at least 80% by .weight of maenesia. silica and .alumina and not more than of lime .ansi in -Whichthere :is .atleast A10% of free magnesio. hzcicoess of the .amount .required to form magnesium orthosili ate with all the silica. andvmegnesium .aluminate with all the .alumina in Vthe granules, ,and .the

second .type consisting .of .a non-.refractory silicate containing a total of at least fby weigtitof sil-ica, magnesiarand alumina, of which'substantially 35 fto 8.2% is silica, .0 to 40% is -magnesia A.and .0 `to :5.0% is alumina, .fthe said intimate ture of Ibasic granular refractory material and :non-refractory silicate `:hav-ing `a weight ratio .of .magnesia .to .silica .and alumina at :least sub.-

`stantially equal to 41.134 times the ysilica 'plus .0.4

mfr-1HE.

REFERENQES .CLTED 

1. A METHOD OF CONSOLIDATING REFRACTORY GRANULAR MATERIAL INTO A MECHANICALLY STRONG AND HIGHLY REFRACTORY PRODUCT WHICH COMPRISES MIXING REFRACTORY GRANULAR PARTICLES CONTAINING A TOTAL OF AT LEAST 80% BY WEIGHT OF MAGNESIA, SILICA AND ALUMINA AND NOT MORE THAN 5% OF LIME, AND IN WHICH THE WEIGHT RATIO OF MAGNESIA TO SILICA AND ALUMINA IS AT LEAST EQUAL TO 1.5 TIMES THE SILICA PLUS 0.5 TIMES THE ALUMINA, WITH NONREFRACTORY MATERIAL CONTAINING A TOTAL OF AT LEAST 75% BY WEIGHT OF SILICA, MAGNESIA AND ALUMINA OF WHICH SUBSTANTIALLY 35 TO 82% IS SILICA, 0 TO 40% IS MAGNESIA, AND 0 TO 50% IS ALUMINA, THE MIXTURE OF REFRACTORY AND NON-REFRACTORY MATERIALS HAVING A WEIGHT RATIO OF MAGNESIA TO SILICA AND ALUMINA AT LEAST SUBSTANTIALLY EQUAL TO 1.34 TIMES THE SILICA PLUS 0.40 TIMES THE ALUMINA, AND HEATING THE MIXTURE TO A TEMPERATURE HIGHER THAN THAT OF INCIPIENT FUSION OF THE NON-REFRACTORY MATERIAL TO FORM LIQUID AND COAT THE PARTICLES OF GRANULAR REFRACTORY MATERIAL AND BY REACTION ELIMINATE THE NON-REFRACTORY SILICATE AND THEREBY BOND THE GRANULES INTO A HIGHLY REFRACTORY AND CONSOLIDATED MASS. 